WO2007123125A1 - Auxiliaire de mise en œuvre et formule pour moulage - Google Patents

Auxiliaire de mise en œuvre et formule pour moulage Download PDF

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Publication number
WO2007123125A1
WO2007123125A1 PCT/JP2007/058344 JP2007058344W WO2007123125A1 WO 2007123125 A1 WO2007123125 A1 WO 2007123125A1 JP 2007058344 W JP2007058344 W JP 2007058344W WO 2007123125 A1 WO2007123125 A1 WO 2007123125A1
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WO
WIPO (PCT)
Prior art keywords
processing aid
fluorine
melt
containing elastomer
molding composition
Prior art date
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PCT/JP2007/058344
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English (en)
Japanese (ja)
Inventor
Tsuyoshi Miyamori
Yoshichika Komiya
Takuya Arase
Original Assignee
Daikin Industries, Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Daikin Industries, Ltd. filed Critical Daikin Industries, Ltd.
Priority to EP07741780A priority Critical patent/EP2011824A4/fr
Priority to US12/297,341 priority patent/US20090082510A1/en
Priority to CN200780013801XA priority patent/CN101426850B/zh
Publication of WO2007123125A1 publication Critical patent/WO2007123125A1/fr
Priority to US13/198,626 priority patent/US20110288221A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2427/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/10—Metal compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/10—Metal compounds
    • C08K3/105—Compounds containing metals of Groups 1 to 3 or of Groups 11 to 13 of the Periodic Table
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/06—Polymer mixtures characterised by other features having improved processability or containing aids for moulding methods
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms

Definitions

  • the present invention relates to a processing aid, a molding composition, a master batch for a processing aid, and a molded article.
  • a method for improving the extrudability of melt processable resin a method of adding a fluorine-containing elastomer as a processing aid to melt processable resin is also known.
  • the fluorine-containing elastomer has the effect of improving the moldability such as the suppression of the occurrence of the melt flattening and the reduction of the extrusion pressure, it is desired to further enhance the effect.
  • Patent Document 1 Japanese Patent Application Laid-Open No. 10-292054
  • the object of the present invention is to provide a processing aid having a high effect of improving moldability when added to a melt processable resin, a molding composition containing the processing aid, and the like. There is to do.
  • the present invention is a processing aid characterized by using a fluorine-containing elastomer that has been heat-treated by adding an alkali metal inorganic salt or an alkaline earth metal inorganic salt.
  • the present invention is a molding composition comprising a melt processable resin and a processing aid, wherein the processing aid also has the processing aid power of the present invention.
  • the present invention is a processing aid masterbatch comprising the melt processable resin (A) and the processing aid of the present invention.
  • the present invention is a molded article obtained by molding the molding composition.
  • the present invention is described in detail below.
  • the fluorine-containing elastomer in the processing aid of the present invention is not particularly limited as long as it is an amorphous fluorine-containing polymer having a fluorine atom bonded to a carbon atom and having rubber elasticity. It may be a known one.
  • the fluorine-containing elastomer generally has 30 to 80% by mass of copolymerized units of the first monomer.
  • the “first monomer” refers to a monomer that constitutes a copolymer unit occupying the largest mass among all copolymer units in the molecular structure of the fluorine-containing elastomer. means.
  • the copolymerized unit is a part of the molecular structure of the fluorine-containing elastomer and means a part derived from the corresponding monomer.
  • a vinylidene fluoride [VDF] unit is a part of the molecular structure of a VDF copolymer and is a part derived from VDF, (CH 2 -CF)
  • the content of the copolymerized unit is obtained by measuring F 19 -NMR.
  • the copolymer unit derived from a monomer other than the first monomer is any one of the monomers copolymerizable with the first monomer. May be derived from only one of them, or may be derived from two or more monomers copolymerizable with the first monomer.
  • Examples of the monomer copolymerizable with the first monomer include fluorine-containing olefins, fluorine-containing burethers and hydrocarbon olefins.
  • the fluorine-containing olefin is not particularly limited, and examples thereof include VDF, tetrafluoroethylene [TFE], hexafluoropropylene [HFP], 1, 2, 3, 3, 3 pentafluoropropene, and black mouth trifluor.
  • VDF tetrafluoroethylene
  • HFP hexafluoropropylene
  • HFP hexafluoropropylene
  • black mouth trifluor examples include polyethylene [CTFE] and fluorinated bur [VF].
  • Examples of the fluorine-containing bull ether include perfluoro (bull ether).
  • Examples of the perfluoro (bulle ether) include perfluoro (alkyl vinyl ether) [PAVE].
  • Examples of the PAVE include, for example, perfluoro (methyl vinyl ether) [PMVE], no fluoro (ethenolevinoleatenole) [PEVE], perfluoro (propyl butyl ether) [PPVE], etc. Those having -6 perfluoroalkyl groups are preferred.
  • the fluorine-containing elastomer scratch, if having a PAVE unit, is preferable that the PAVE units is 20 to 40 mass 0/0 of the total copolymer units! /,.
  • the hydrocarbon olefin is not particularly limited, but for example, force propene including ethylene, propene and the like is preferable.
  • the hydrocarbon olefin unit is preferably 4 to 20% by mass of the total copolymer units.
  • fluorine-containing elastomer examples include, for example, TFE / perfluoro (bull ether) copolymer, VDFZHFP copolymer, VDFZCTFE copolymer, VDFZTFE copolymer, VDFZHFPZTFE copolymer, VDFZCTFEZTFE system.
  • TFE / perfluoro (bull ether) copolymer examples include, for example, TFE / perfluoro (bull ether) copolymer, VDFZHFP copolymer, VDFZCTFE copolymer, VDFZTFE copolymer, VDFZCTFEZTFE system.
  • VDF copolymer whose first monomer is VDF is VDF
  • VDF copolymer which is preferably a TFE copolymer in which the first monomer is TFE, is more preferable.
  • VDF / HFP copolymer and VDFZTFE ZHFP copolymer are more preferable, and VDFZHFP copolymer is more preferable.
  • the processing aid of the present invention may be composed of only one type of fluorine-containing elastomer, or may be composed of two or more types of fluorine-containing elastomer! /.
  • the fluorine-containing elastomer has a number average molecular weight [Mn] force of generally 13000 to 470000.
  • the number average molecular weight is measured by gel permeation chromatography described later.
  • the processing aid of the present invention is a fluorine-containing elastomer that has been heat-treated by adding an alkali metal inorganic salt or an alkaline earth metal inorganic salt (hereinafter sometimes referred to as "specific metal inorganic salt" t). Is used.
  • the fluorine-containing elastomer can be prepared by a conventionally known method except that the specific metal inorganic salt is added and heat-treated.
  • Examples of the process other than the heat treatment include the above-mentioned fluorine Polymerization of contained monomer and non-fluorine-containing monomer to be added if necessary, post-treatment (dilution, concentration, purification, etc.) of the obtained fluorine-containing elastomer aqueous dispersion performed as necessary, the fluorine-containing elastomer monoaqueous Coagulation of the dispersion or the post-treatment dispersion, drying of the fluorine-containing elastomer coagulum obtained by the coagulation (sometimes referred to as crumb), fluorine-containing obtained by the drying Elastomer pulverization and the like can be mentioned, and the conditions of each step can be appropriately selected according to each material to be used and the kind and amount of the desired fluorine-containing elastomer.
  • Examples of the metal constituting the specific metal inorganic salt include magnesium, lithium, sodium, potassium, calcium, and sodium.
  • the specific metal inorganic salt is not particularly limited, but alkali metal nitrate is more preferable even when alkali metal nitrate or alkali earth metal nitrate is preferred.
  • alkali metal nitrate examples include sodium nitrate and potassium nitrate.
  • the alkaline earth metal nitrate that potassium nitrate is preferable includes, for example, magnesium nitrate.
  • the specific metal inorganic salt is preferably added so that the mass thereof corresponds to 20 to 2000 ppm of the fluorine-containing elastomer.
  • the amount of the additive added is preferably an amount corresponding to lOOppm of the fluorine-containing elastomer at a preferred lower limit, and an amount corresponding to lOOOppm of the fluorine-containing elastomer.
  • the specific metal inorganic salt may be added in the form of a solid, but is preferably added in the form of an aqueous solution in terms of uniform dispersion.
  • the specific metal inorganic salt may be added so that the specific metal inorganic salt coexists with the fluorine-containing elastomer at the time of heat treatment in the present invention.
  • the specific metal inorganic salt is an electrolyte
  • the addition is considered to be preferable after polymerizing the fluorine-containing monomer and the fluorine-free monomer added as necessary in the step of preparing the fluorine-containing elastomer.
  • the fluorinated elastomer monoaqueous dispersion obtained by the polymerization may be carried out.
  • the fluorinated elastomer monoaqueous dispersion may be used if necessary.
  • the additive of the specific metal inorganic salt is, among others, when drying (4), kneading (5), or preparing a master batch for a processing aid (6). It is more preferable to perform the drying in the above (4) from the viewpoint that the heat treatment is preferably performed sufficiently.
  • the heat treatment in the present invention may be performed at any time of the above-mentioned (1) to (6) as long as the specific metal inorganic salt is added or after the addition. In view of this, it is preferable to carry out the drying in the above (4) or the preparation of the master batch for a processing aid in the above (6).
  • the pulverized product preferably has an average particle size of 5 ⁇ m to 5 mm! /.
  • the average particle diameter is more preferably a lower limit of 200 m and a more preferable upper limit of 3 mm.
  • the average particle diameter is a value measured according to JIS K 6891-1995.
  • the average particle size (d50) is the cumulative percentage (%) of the weight of the particles obtained by classifying the particle size from the measurement result of the particle size distribution performed in accordance with JIS K 6891-1995. Is plotted on a logarithmic graph, and the cumulative percentage: 50% particle diameter is read, or a straight line is obtained by the least square method and 50% particle diameter is calculated.
  • the heat treatment in the present invention applies a shearing force, and performs heating and kneading. By applying the shearing force in the heat treatment, the specific metal inorganic salt is sufficiently kneaded in the fluorine-containing elastomer.
  • the shearing force due to the kneading can be given by, for example, putting it into an extruder such as a twin screw extruder and performing extrusion.
  • the operation of applying the heat and shearing force is performed, for example, when the drying step after the coagulation of the fluorine-containing elastomer is performed using an extruder, during the kneading of the fluorine-containing elastomer in the extruder.
  • specific metal inorganic salts can be mixed together at the time of kneading the fluorine-containing elastomer in an extruder such as a twin-screw extruder for the production of a master batch described later. It can also be done.
  • the conditions for each operation can be appropriately set according to the composition, amount, etc. of the dispersion or coagulum to be heat treated.
  • the temperature of the heat treatment may be within a temperature range that does not cause thermal degradation of the fluorine-containing elastomer, but is preferably 120 to 200 ° C.
  • the temperature is more preferably a lower limit force S140 ° C, and a more preferable upper limit is 180 ° C.
  • the heat treatment is generally performed for 2 to 20 minutes, preferably 5 to L0 minutes.
  • the processing aid of the present invention may further contain an additive such as an anti-sticking agent in addition to the fluorine-containing elastomer that has undergone the above heat treatment.
  • an anti-sticking agent is added, the above-mentioned fluorinated elastomer pulverized product can be prevented from sticking to each other.
  • the processing aid of the present invention is added to the melt processable resin, the dispersion of the fluorinated elastomer particles is prevented. Sex can be further improved.
  • the anti-sticking agent is not particularly limited.
  • plasticizers such as dioctyl phthalate and diglysyl phthalate; fillers such as talc, graphite and silica; titanium oxide, iron oxide, molybdenum oxide Colorants such as magnesium oxide, calcium oxide, lead oxide Acid agents; heat stabilizers such as calcium stearate and magnesium stearate; interfacial agents such as polyethylene glycol and poly-strength prolatatone; and the like.
  • talc calcium carbonate, etc., which are preferred as fillers, are more preferred.
  • the amount of the anti-sticking agent can be appropriately set according to the type, amount and the like of the fluorine-containing elastomer used, but generally 100 parts by mass of the fluorine-containing elastomer is used.
  • the amount is preferably 1 to 15 parts by mass, and less in amount.
  • the amount for obtaining the minimum necessary effect as the anti-sticking agent is preferably 2 parts by mass or more, more preferably 4 parts by mass or more with respect to 100 parts by mass of the fluorine-containing elastomer. More preferred is 10 parts by mass or less.
  • the processing aid of the present invention can be used by adding to melt-processable rosin.
  • the processing aid of the present invention is excellent in dispersibility in melt-processable resin.
  • melt-processable resin lmn!
  • lmn a fluorine-containing elastomer particle having an average particle diameter of about 2 m in the melt processable resin, but it is 10 m or more and less than 1000 m.
  • processing aid particles having an average particle diameter of about 1 ⁇ m in the melt processable resin, and therefore the latter finely pulverized product is preferable.
  • the fluorine-containing elastomer that has undergone the above-mentioned heat treatment even if it is a finely pulverized product, has a mean particle diameter of 3 to about L0 m depending on the capability of the extruder. Particles may be dispersed in the melt processable resin.
  • the processing aid of the present invention can sufficiently exhibit the moldability improving effect inherent in the fluorine-containing elastomer as compared with the conventional processing aid.
  • the processing aid of the present invention comprises a fluorine-containing elastomer to which an alkali metal salt or an alkaline earth metal salt is added and has undergone the above-described heat treatment. More excellent in the effect of improving the moldability of melt processable resin.
  • the copolymer composition has the same fluorine-containing elastomer, and the inorganic salt is not added. In comparison, the extrusion pressure can be reduced and the melt fracture can be eliminated in a short time. For this reason, the processing aid of the present invention is very useful as a material for molding compositions and master batches for processing aids.
  • the molding composition of the present invention comprises a melt processable resin and the above-mentioned processing aid of the present invention.
  • the melt strength resin means a polymer that can measure the melt flow at a temperature higher than the crystallization melting point according to ASTM D-1238 and D-2116.
  • the melt-processable resin is not particularly limited, and is preferably a resin containing no fluorine.
  • polyolefin resin such as polyethylene and polypropylene; nylon 6, nylon 11, nylon 12, Polyamide [PA] resin such as nylon 46, nylon 66, nylon 610, nylon 612, nylon MXD6; polyethylene terephthalate [PET], polybutylene terephthalate [PBT], polyarylate, aromatic polyester (including liquid crystal polyester) Polyester, such as polycarbonate [PC]; Polyacetal [POM] resin; Polyether-polyoxyl [PPO], Polyether ether such as modified polyphenylene ether, Polyetheretherketone [PEEK]; Polyamide, such as polyaminobismaleimide Imide [PAI] resin; Polysulfone [PSF], Polyether Polysulfone-based resins such as sulfone [PES]; the power of bully polymers such as ABS resin, poly-4-methylpentene-1 (TPX resin), polyphenylene-(
  • melt-processable resins polyolefin resin, polyolefin resin, which is preferable, is more preferable.
  • the melt processable resin in the molding composition is preferably a thermoplastic resin from the viewpoint of easy melt molding.
  • melt processable resin may be used alone or in combination of two or more.
  • the melt processable resin preferably has a melt casing temperature of 100 to 350 ° C. Further, the melt processable resin may have crystallinity or may not have crystallinity. [0046] When the melt processable resin has crystallinity, a melting point of 80 to 300 ° C is preferred, and a melting point of 100 to 200 ° C is more preferred! /.
  • the melt processable resin having no crystallinity preferably has a processing temperature almost equal to that of the melt processable resin having crystallinity and a melting point range.
  • the melt processable resin can be synthesized by a conventionally known method or the like according to each type.
  • the melt processable resin may be a powder, granule, pellet, or the like, but in the resulting molding composition, the melt processable resin is efficiently melted and the processing aid is dispersed. Pellet is preferred because it can be used! /.
  • the heat-treated fluorine-containing elastomer contained in the processing aid is 0.005 to 5 in total of the total mass of the melt-processable resin and the mass of the fluorine-containing elastomer. It is preferable that it is mass%.
  • the fluorine-containing elastomer is more preferably 0.01% by mass or more of the total mass of the melt-processable resin and the mass of the fluorine-containing elastomer, and is 0.5% by mass or less. I prefer to be more!
  • the molding composition may be prepared by adding the processing aid of the present invention itself to the melt processable resin, or the melt calorie as a master batch for the processing aid described later. It may be prepared in addition to natural rosin.
  • the molding composition of the present invention may be blended with other components, if necessary, in addition to the processing aid and the melt processable resin.
  • the other components are not particularly limited.
  • reinforcing materials such as glass fiber and glass powder; stabilizers such as minerals and flakes; lubricants such as silicone oil and molybdenum disulfide; pigments; carbon black Conductive agents such as rubber; impact resistance improvers such as rubber; other additives such as polyolefins, which are established as voluntary standards by the Sanitation Council for Polyolefins, etc., can be used.
  • the master batch for processing aid of the present invention comprises the melt processable resin (A) and the processing aid of the present invention described above.
  • the master notch for processing aid of the present invention can be suitably used as a processing aid when molding the melt processable resin (A).
  • the master notch for processing aid of the present invention is one in which the fluorine-containing elastomer is evenly dispersed in the melted caloric resin (A), so it is added at the time of molding the melt processable resin. Can improve molding processability such as reduction in extrusion torque and extrusion pressure.
  • melt-processable resin (A) examples include those similar to the above-described melt-processable resin, and among them, a polyethylene resin that is preferably a polyolefin resin is preferable. It is preferable.
  • the processing aid particles in the processing aid master batch have an average particle size of generally 0.
  • It is preferably 01 to 10 / ⁇ ⁇ , and more preferably 0.1 to 2 / ⁇ ⁇ .
  • the master batch for processing aid of the present invention may be in any form such as powder, granule, pellet, etc., but the heat-treated fluorine-containing elastomer is fine in the melt-processable resin (soot). In terms of being held in a dispersed state, it is preferably a pellet by melt kneading.
  • the fluorine-containing elastomer has a mass of the melt-processable resin (pox) and the fluorine-containing elastomer in terms of facilitating melt molding described later. It is preferably more than 0.5% by mass and not more than 20% by mass of the total mass.
  • the master batch for a processing aid of the present invention may be formed by blending other components, if necessary, with the processing aid and the melt-processable resin (foam).
  • the other components are not particularly limited, and examples thereof include those described in the molding composition of the present invention.
  • a master batch for a processing aid of the present invention is obtained by adding a fluorine-containing elastomer constituting the processing aid, the above-described inorganic salt, and, if necessary, an anti-sticking agent, etc. to melt-processable resin (resin).
  • melt-processable resin resin
  • the above-mentioned processing aid prepared in advance is added to the melt-processable resin (A). What is obtained by kneading what was obtained at this temperature is preferable.
  • the processing aid masterbatch is obtained because it is easy to disperse in the melt processable resin. For example, it is difficult to cause poor appearance such as a gel-like lump in a flat film or an inflation film.
  • the molded article of the present invention is formed by molding the above-described molding composition of the present invention.
  • the molding composition of the present invention may be prepared in advance and charged into a molding machine to perform melting, extrusion, etc., or the above processing aid and melt processable resin may be molded. It may be one that is simultaneously injected into a machine to perform melting, extruding, etc., or the above-mentioned processing aid master batch and melt processable resin are simultaneously introduced into a molding machine for melting, extruding, etc. You may do it.
  • Molding of the molding composition is not particularly limited and includes, for example, extrusion molding, injection molding, blow molding, and the like. Among them, in order to effectively exhibit the molding processability. Is preferably extrusion molding.
  • Various conditions relating to the molding are not particularly limited, and can be appropriately set according to the composition and amount of the molding composition to be used, the shape and size of the desired molded product, and the like.
  • the molding temperature is generally not less than the melting point of the melt processable resin in the molding composition, and is lower than the decomposition temperature of the processing aid and the melt processable resin. Perform at temperature and range from 100 to 350 ° C.
  • the molding temperature may be referred to as extrusion temperature.
  • the molded body of the present invention can be formed into various shapes such as, for example, a sheet shape; a film shape; a rod shape; a pipe shape;
  • the use of the molded body is not particularly limited, and depends on the type of melt-processable resin used. For example, it is suitably used for mechanical properties and other mechanical properties that are mainly strongly required. It is done.
  • Applications of the molded body include, for example, various films, bags, coating materials, food containers such as beverage containers, cables, pipes, fibers, bottles, gasoline tanks, and other various industrial molded products. Can be mentioned.
  • the processing aid and the master notch for the brute aid of the present invention have the above-described configuration, the effects of improving the molding processability such as the reduction of the extrusion pressure and the suppression of the melt fracture are conventional. Higher than stuff. Since the molding composition of the present invention is the above-mentioned processing aid, it is excellent in molding caloricity, and the molded product of the present invention is formed by molding the molding composition. Therefore, it is excellent in mechanical properties such as mechanical properties.
  • the amount of the composition in each example and each comparative example is based on mass unless otherwise specified.
  • Each measured value described in each example and each comparative example is a value obtained by the following method.
  • Measuring device LS-8000 (manufactured by Tosoh Corporation)
  • TSK guard column HXL— H TSK gel G4000HXL, TSK gel G
  • the melt fracture rate was determined by the following procedure.
  • the crumb obtained from the praying was transferred to a twin-screw extruder (TEM75; manufactured by Toshiba Machine Co., Ltd.), and dried by extrusion under the following conditions.
  • the KNO treatment concentration was equivalent to 400 ppm of the mass of FKM after drying.
  • the obtained FKMZKNO composite was subjected to a cutter-type coarse pulverizer (Rapid R1528, manufactured by Rikita Corporation).
  • the FKM coarsely pulverized product having an average particle diameter of 1 to 3 mm was obtained.
  • the above FKM coarsely pulverized product 4 Og was coated with 4 g of talc to obtain a processing aid.
  • LDPE low density polyethylene
  • the fluorine-containing elastomer in the processing aid masterbatch was dispersed as particles having an average particle diameter of 1 to 2 ⁇ m (see FIG. 1).
  • Short shaft extruder (VS30-26 type extruder manufactured by Tanabe Plastics, LZD: 26, screw diameter: 30 mm) and inflation die (die diameter 60 mm, die gap 0.5 mm manufactured by Tanabe Plastics) was added, and linear low-density polyethylene (metallocene LLDPE) (product name: Evolue SP2520, manufactured by Prime Polymer Co., Ltd.) using a metal mouth catalyst was added, and extrusion continued for about 1 hour under the following extrusion conditions. The extrusion pressure was stable at around 38 MPa, and it was confirmed that melt fracture occurred on the entire extruded film surface without change.
  • metal mouth catalyst linear low-density polyethylene
  • the time for discharging the metal throat LLDPE staying in the extruder is about 5 minutes after the start of the charging, and after about 5 minutes from the start of the charging, the extrusion pressure starts to decrease and the melt fracture decreases. Began to do. 20 minutes after the start of charging, the melt fracture disappeared completely, and the extrusion pressure decreased to 38. OMPa force and 36. OMPa.
  • Figure 2 shows the measurement results for melt fracture.
  • the extruder was purged with a mixture of the above-mentioned meta-mouth cene LLDPE and 1% by mass of talc after the above-described extrusion evaluation, and then purged by adding the above-mentioned meta-mouth sen LLDPE alone. .
  • Each purge was extruded for about 4 hours continuously under the same conditions as in the above-mentioned extrusion evaluation, and finished after confirming that the extrusion pressure had returned to the original state.
  • FKM fluorine-containing elastomer
  • VDF zi-lidene fluoride
  • HFP hexafluoropropylene
  • an FKM coarsely pulverized product having an average particle size of 1 to 3 mm was obtained.
  • the FKM coarsely pulverized product is further pulverized by a disk-type fine pulverizer to form an FKM powder product having an average particle diameter of 500 ⁇ m. Obtained.
  • a processing aid masterbatch was prepared in the same manner as in Example 1 except for the above, and extrusion evaluation was performed. About 6 minutes after the start of charging the molding composition, the extrusion pressure began to decrease and the melt fracture began to decrease. After 15 minutes from the start of the charging, the melt fracture disappeared completely, and the extrusion pressure decreased from 38.2 MPa to 35.6 MPa.
  • Table 1 shows the measurement results of extrusion pressure and melt fracture.
  • the fluorine-containing elastomer in the processing aid masterbatch was dispersed as particles having an average particle diameter of about 1 ⁇ m (see Fig. 3).
  • the FKM crumb used in Example 1 was transferred to an extruder without adding KNO aqueous solution and dried.
  • This FKM was pulverized with a cutter type coarse pulverizer (Rapid R1528, manufactured by Rikita Co., Ltd.) to obtain an FKM coarsely pulverized product having an average particle diameter of 1 to 3 mm. Place 50 g of this FKM coarsely pulverized product and a solution of 0.025 g of KN 2 O in 2 ml of pure water into a glass container (supplied with the mixer).
  • a cutter type coarse pulverizer Rapid R1528, manufactured by Rikita Co., Ltd.
  • a mixer (Milcer IFN-300DG; manufactured by IWATANI) was assembled and mixed in the glass container at room temperature (23 ° C) for 1 minute to obtain an FKMZKNO composite.
  • the obtained KNO-treated FKM40g is coated with 4g of talc so that the amount of FKM is 2% by mass.
  • the master batch for the resulting strength additive was weighed so that the FKM amount was 500 ppm, and blended with Metaguchisen LLDPE (product name: Evolue SP2520, manufactured by Prime Polymer Co., Ltd.).
  • the molding composition was put into a hopper of the above extruder, and extrusion evaluation was performed in the same manner as in Example 1.
  • the fluorine-containing elastomer used in Example 2 was pulverized with a cutter-type coarse pulverizer (Rapid R1528, made of potato clay) to obtain an FKM coarsely pulverized product having an average particle diameter of 1 to 3 mm. 50 g of this FKM coarsely pulverized product and a solution obtained by dissolving 0.025 g of KNO in 2 ml of pure water were placed in a glass container (mixer
  • a mixer (Milcer IFN-300DG; manufactured by IWATANI) was assembled and mixed in the glass container for 1 minute to obtain an FKM / KNO composite.
  • the FKM finely pulverized product was obtained by pulverizing with a cutter type pulverizer.
  • the obtained FKM finely pulverized product was used in the same manner as the KNO-treated FKM in Example 3 for a power builder.
  • a star batch was prepared.
  • Example 2 Using the obtained master batch for processing aid, evaluation of inflation film extrusion was carried out in the same manner as in Example 1. Immediately after the injection, the extrusion pressure was 38. OMPa, 15 minutes after the injection, the melt fracture disappeared completely, and the extrusion pressure dropped to 35.2 MPa.
  • Example 4 The same as in Example 4 except that the KNO loading was changed to an amount equivalent to lOOppm of FKM.
  • the extrusion was evaluated. The melt fracture disappeared 15 minutes after charging, but it reappeared 20 minutes after charging and disappeared completely 30 minutes after charging. The extrusion pressure dropped from 38. OMPa to 35.6 MPa.
  • Example 4 The same as in Example 4 except that the KNO loading was changed to an amount equivalent to lOOOOppm of FKM.
  • extrusion evaluation was started.
  • the FKM content in the molding composition is 500 ppm
  • the melt flattening does not disappear completely even after 30 minutes, and when the FKM content is increased to 750 ppm and evaluation is continued, the total extrusion time is 28 minutes. 58 minutes).
  • the extrusion pressure was reduced to 36.4 MPa from 37.9 MPa force when the FKM amount in the forming yarn and the composite was 500 ppm, and decreased to 36. OMPa by increasing the FKM amount by 750 ppm.
  • a nail was prepared and evaluated for extrusion.
  • a master bar for processing aids was used in the same manner as in Example 4 except that KCO was used instead of KNO.
  • a nail was prepared and evaluated for extrusion.
  • the melt fracture does not disappear completely even after 30 minutes.
  • the FKM amount in the molding composition was 500 ppm, the extrusion pressure decreased to 37. IMPa force and so on to 36. OMPa, and to 35.4 MPa by increasing the FKM amount to 750 ppm.
  • a master notch for processing aids was produced in the same manner as in Example 1 except that extrusion was performed without adding 3 and drying.
  • the fluorine-containing elastomer in the obtained master batch for force aid was dispersed as particles having an average particle diameter of about 1 to 7 ⁇ m (see FIG. 4).
  • Example 1 the molding composition of Example 1 containing a processing aid subjected to a heat treatment by adding KNO
  • a master batch was prepared.
  • the fluorine-containing elastomer contained in the obtained master batch for power aid was dispersed as particles having an average particle diameter of about 1 to 4 ⁇ m! /, (FIG. 5).
  • Example 2 the molding composition of Example 2 containing a processing aid that was heat-treated by adding KNO.
  • the melt fracture can be completely erased in about 15 to 20 minutes after the start of charging, but the molding composition of Comparative Example 2 containing the processing aid obtained without the heat treatment has passed 1 hour. Even so, it was found that about 37% of the melt fracture remained.
  • a master batch for a brute aid was prepared in the same manner as in Example 3 except that KNO treatment was not performed.
  • the starting force of the molding composition started to decrease, and the melt fracture started to decrease.
  • the melt fracture did not disappear even 30 minutes after the start of the addition, and the extrusion pressure decreased only to 38.4 MPa from 38.2 MPa.
  • the FKM amount after mixing is measured so that it corresponds to 750 ppm of the molding composition, and a master batch for processing aid is prepared. Added more. Even after 30 minutes (60 minutes after the start of addition), the melt fracture did not disappear completely, and the extrusion pressure was reduced to 37.2 MPa.
  • the processing aid and the master notch for a powering aid of the present invention have the above-described configuration, conventional effects such as reduction of extrusion pressure and suppression of melt fracture have been achieved. taller than. Since the molding composition of the present invention is the above processing aid, it is excellent in molding processability, and the molded product of the present invention is formed by molding the molding composition. Therefore, it is excellent in mechanical properties such as mechanical properties.
  • FIG. 1 is an optical micrograph showing a dispersion state of a processing aid in a processing aid master batch in Example 1.
  • FIG. 2 shows the measurement results of melt fracture in Example 1 and Comparative Example 1.
  • FIG. 3 is an optical micrograph showing the dispersion state of the processing aid in the processing aid master batch in Example 2.
  • FIG. 4 is an optical micrograph showing the dispersion state of the processing aid in the processing aid master batch in Comparative Example 1.
  • FIG. 5 is an optical micrograph showing the dispersion state of the processing aid in the processing aid master batch in Comparative Example 2.

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  • Chemical Kinetics & Catalysis (AREA)
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Abstract

La présente invention a pour objet un auxiliaire de mise en œuvre qui présente un effet élevé d'amélioration de capacité de mise en œuvre par moulage lorsqu'il est ajouté dans une résine transformable à l'état fondu. La présente invention a également pour objet une formule pour moulage, etc., contenant un tel auxiliaire de mise en œuvre. La présente invention concerne spécifiquement un auxiliaire de mise en œuvre caractérisé en ce qu'il emploie un élastomère fluoré qui est thermiquement traité par ajout d'un sel inorganique de métal alcalin ou d'un sel inorganique de métal alcalino-terreux.
PCT/JP2007/058344 2006-04-18 2007-04-17 Auxiliaire de mise en œuvre et formule pour moulage WO2007123125A1 (fr)

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EP07741780A EP2011824A4 (fr) 2006-04-18 2007-04-17 Auxiliaire de mise en oeuvre et formule pour moulage
US12/297,341 US20090082510A1 (en) 2006-04-18 2007-04-17 Polymer processing additive and molding composition
CN200780013801XA CN101426850B (zh) 2006-04-18 2007-04-17 加工助剂和成型用组合物
US13/198,626 US20110288221A1 (en) 2006-04-18 2011-08-04 Polymer processing additive and molding composition

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JP2006114921A JP2009155357A (ja) 2006-04-18 2006-04-18 加工助剤及び成形用組成物

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DE102008042906A1 (de) * 2008-10-16 2010-04-22 Rhein-Chemie Rheinau Gmbh Säulenpresse zur Qualitätsanalyse
US11274172B2 (en) * 2009-08-27 2022-03-15 Daikin Industries, Ltd. Processing additive, molding composition masterbatch of processing additive and molding article
CN104136525B (zh) 2012-02-24 2016-05-25 日本聚丙烯株式会社 丙烯-乙烯共聚物树脂组合物以及其成形体、膜和片材
US20160311954A1 (en) * 2013-12-26 2016-10-27 Daikin Industries, Ltd. Processing aid for polyolefins, and polyolefin composition
KR102345907B1 (ko) * 2014-06-18 2022-01-03 쓰리엠 이노베이티브 프로퍼티즈 캄파니 광 투과성 플루오로중합체 조성물 및 물품
JP6308059B2 (ja) * 2014-07-15 2018-04-11 ダイキン工業株式会社 成形用組成物の製造方法、及び、成形品の製造方法
KR102235114B1 (ko) * 2019-11-08 2021-04-01 한화토탈 주식회사 절연재 제조용 수지 조성물 및 이를 이용한 전력 케이블

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US20110288221A1 (en) 2011-11-24
CN101426850A (zh) 2009-05-06
US20090082510A1 (en) 2009-03-26
JP2009155357A (ja) 2009-07-16
EP2011824A1 (fr) 2009-01-07
EP2011824A4 (fr) 2011-06-29

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